Explosives comprising modified copolymers of polyisobutylene and maleic anhydride as emulsifiers

ABSTRACT

A terpolymer comprising monomer units derived from an olefin having more than 40 carbon atoms, maleic anhydride, and an alkylallyl polyglycol ether of the formula 
     
       
         R—(OCH 2 CH 2 ) n O—CH 2 —CH═CH 2   
       
     
     where n=3-20 and R=C 1 -C 4 -alkyl.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of German patent application 198 47868.2, filed Oct. 16, 1998, and U.S. patent application Ser. No.09/419,215, filed Oct. 15, 1999 now U.S. Pat. No. 6,516,840.

BACKGROUND OF THE INVENTION

Of the explosives used worldwide today, the ammonium nitrate explosivesare the largest group. They are widespread particularly in mining. Aparticularly important group within the ammonium nitrate explosives inthis connection are the emulsion explosives, which consist essentiallyof a water-(or salt)-in-oil emulsion of an aqueous solution,supersaturated at room temperature, in an oil matrix (fuel). The oilphase is the continuous phase and includes small droplets of thesupersaturated solution of the oxidizing agent. In this connection, thewater content of the solution can be up to below 4% by weight. Thedissolved salts are metastable and have a tendency towardcrystallization. If, for example, ammonium nitrate crystals form, thishas unfavorable effects on the emulsion (solidification, the emulsion isno longer pumpable) and also on the cap sensitivity of the emulsion,i.e. the explosive becomes less sensitive to initial detonation. Inorder to keep such an emulsion stable, therefore, an emulsifier isgenerally required which is suitable for the preparation of water-in-oilemulsions. Because of its surface activity, it promotes emulsificationof the salt phase in small droplets and prevents coalescence of theformed droplets after the emulsion has formed.

The emulsion, also called matrix, is generally still not ignitable, andtherefore, in order to achieve sufficient cap sensitivity, the densityof the matrix must be lowered by adding microspheres (glass bubbles), bychemical gassing or by another method, such as, for example, by addinggranular ammonium nitrate. The emulsions are then in some circumstancesalso ignitable without boosters with blasting caps. Such emulsions aresafety explosives. This technology was described for the first time inU.S. Pat. No. 3,447,978.

U.S. Pat. No. 3,447,978 discloses explosive emulsions consisting of asalt-in-oil emulsion of a supersaturated ammonium nitrate solution in anoil matrix, an emulsifier of the water-in-oil type, e.g. a sorbitanester, fatty acid glycerides or phosphoric esters, being used asemulsifiers. These emulsifiers, however, only give emulsions with lowlong-term stability.

EP-A-0 155 800 discloses emulsion explosive material mixtures whichcomprise emulsifiers, where at least one emulsifier is stronglylipophilic and an agent for altering the electrical conductivity of theemulsion, which essentially consists of a lipophilic and of ahydrophilic component, and in which the lipophilic constituent has achain structure derived from a polymer of a monoolefin containing 3-6carbon atoms. In particular, reaction products ofpoly(isobutenyl)succinic anhydride with aminoalcohols, amines andsorbitol as emulsifiers are described.

EP-A-0 285 608 discloses water-in-oil emulsions, where the emulsifierspresent are reaction products of a hydrocarbon-substituted carboxylicacid or a hydrocarbon-substituted anhydride (or an ester or amidederived therefrom) with ammonia or at least one amine, the hydrocarbonradical having on average 20-500 carbon atoms. Polymers containing twoor more hydrocarbon radicals are not disclosed. Reaction products ofpoly(isobutenyl)succinic anhydrides with morpholine and aminoalcoholsare specifically described.

The emulsifiers cited in EP-A-0 155 800 and EP-A-0 285 608 and based onpolyisobutenylsuccinic anhydride (i.e. the reaction product of along-chain, branched olefin with maleic anhydride), produce, in contrastto the emulsifiers of the first generation cited in U.S. Pat. No.3,447,978, emulsions with high long-term stability. The baseemulsifiers, however, have the disadvantage that their synthesis,because of the underlying ene reaction, requires very high temperatures(180-230° C.) and relatively long reaction times, which leads to a highconsumption of energy and correspondingly high preparation costs.

Polymers of polyisobutylene and maleic anhydride are also part of theprior art.

WO-A-90/03359 discloses polymers of polyisobutylene and maleic anhydridewhich, after they have been functionalized using polyamines, can be usedas additives in fuels and lubricating oils. EP-A-0 831 104 disclosesterpolymers of polyisobutylene, α-olefins and maleic anhydride and alsoreaction products of these terpolymers with polyamines for analogousapplications.

SUMMARY OF THE INVENTION

Surprisingly, we have now found that not only derivatives of monomericadducts of polyisobutylene and maleic anhydride, but also derivatives ofpolymeric adducts of maleic anhydride and olefins having 20-500 carbonatoms, alone or mixed with other emulsifiers, are suitable as extremelyeffective emulsifiers for emulsion explosives. In contrast to thecompounds cited in EP-A-0 155 800 and EP-A-0 285 608, these compoundshave two or more hydrophobic groups and two or more hydrophilic headgroups on the polymer backbone. The parent polymeric anhydrides can beprepared at a significantly lower temperature (80-150° C.) and byfree-radical copolymerization significantly more quickly than thealkenylsuccinic acid derivatives of the prior art, meaning that theyhave ecological and also economic advantages over the prior art.Surprisingly, despite having molecular weights which are significantlyhigher than those of polyisobutenylsuccinic acid derivatives, theproducts do not have increased viscosities, meaning that the productscan be handled without problems despite the relatively high molecularweight. In this connection, the emulsifying action and emulsionstability of the products, particularly in mixtures with small amountsof coemulsifiers, correspond to at least those of the products cited inthe prior art.

The invention thus provides an explosive composition consisting of

A) an oxygen-donating constituent, which forms a disperse phase,

B) an organic constituent, which forms a dispersion phase, and

C) at least one emulsifier,

wherein the emulsifier includes a copolymer comprising, in random orregular order, structural units derived from maleic anhydride and fromone or more olefins having more than 40 carbon atoms, where thestructural units derived from maleic anhydride have been modified byreaction with alcohols, aminoalcohols, ammonia or amines.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the text below, the term “maleic anhydride” also refers to the maleicanhydride modified in the sense given above by reaction with alcohols,aminoalcohols, ammonia or amines.

The emulsifier according to the invention comprises, in the copolymerchain, at least one olefin, preferably an α-olefin having more than 40,preferably from 40 to 500, in particular from 40 to 200, carbon atoms.The copolymer may also further comprise other comonomers.

Suitable olefins for the preparation of the polymers according to theinvention are olefins preferably containing a double bond in theα-position or mixtures of the number of such olefins. Particularpreference is given to olefins obtained by polymerization ofC₂-C₆-monoolefins, such as, for example, polypropylenes orpolyisobutylenes in the molecular weight range from, preferably,200-5000 g/mol, and which comprise >30%, preferably >50%, particularlypreferably >70%, of isomers containing a double bond in the α-position,i.e., for example, containing an end group R—C(═CH₂)CH₃. Suchpolyisobutylene grades are obtainable, for example, under the tradenames Glissopal® or Ultravis®. In this connection, particularly suitablepolyisobutylenes are those which have a high content of isomerscontaining an α-position double bond. Particularly suitable as olefincomponents are also mixtures of polyisobutylenes and straight-chain orbranched-chain C₁₀-C₃₀-α-olefins or mixtures of polyisobutylenes withalkylallyl polyglycol ethers having from 3 to 20 ethylene oxide units.In this case terpolymers of polyisobutylene, maleic anhydride andα-olefin or allylmethyl polyglycol ethers form. The alkylallylpolyglycol ethers mentioned are preferably allylmethyl polyglycol ethersin the molecular weight range from 200 to 1000 g/mol.

The emulsifiers according to the invention can be synthesized by methodsknown per se, one description being, for example, in Oil Gas EuropeanMagazine 1996, 22, 38-40. Firstly, olefins, preferably α-olefins,particularly preferably polyisobutylene or mixtures of polyisobutyleneand short-chain C₁₀-C₃₀-α-olefins or mixtures of polyisobutylene withallylalkyl polyglycol ethers and maleic anhydride are polymerized usinga suitable free-radical initiator. The molar quantity ratio betweenmaleic anhydride and the total of the other comonomers is preferablyfrom 0.7:1 to 1.6:1. The polymerization can be carried out without adiluent, or also in a nonprotic solvent. The reaction temperature of thepolymerization is between 50 and 200° C., preferably between 80 and 160°C. Alternating copolymers of olefin and maleic anhydride preferablyform. In the second reaction step, the resulting polymer is reacted in apolymer-analogous reaction with alcohols or aminoalcohols to givepolymeric half-esters, with ammonia and/or amines and, whereappropriate, also with aminoalcohols, to give polymeric half-amides orimides.

Suitable alcohols for the functionalization of the maleic anhydridecopolymers to give half-esters are monoalcohols having 1-6 carbon atoms,e.g. methanol, ethanol, propanols, butanols or pentanols;alkylpolyglycols are also suitable.

Suitable aminoalcohols are, for example, N,N-dimethylaminoethanol,N,N-diethylaminoethanol, N,N-dibutylaminoethanol,3-dimethylaminopropanol, N-hydroxyethylmorpholine, monoethanolamine,diethanolamine, triethanolamine, 3-aminopropanol, isopropanolamine and2-(2-aminoethoxy)ethanol. The half-ester formation is carried out at 30to 150° C., preferably at 50 to 100° C. In order to avoid crosslinkingreactions, aminoalcohols with a tertiary amine nitrogen and a hydroxylfunction, such as dimethylaminoethanol, diethylaminoethanol orN-hydroxyethylmorpholine, are particularly preferred.

Suitable amines for the functionalization of the maleic anhydridecopolymers are monoamines with a primary or secondary amino function,such as methylamine, ethylamine, butylamine, laurylamine, coconut fattyamine, stearylamine, dimethylamine, diethylamine, dibutylamine etc., butalso di- and polyamines, e.g. 3-dimethylaminopropylamine,3-diethylaminopropylamine or 3-morpholinopropylamine.

Preferred amines contain only one condensable alcohol or amino group inorder to prevent crosslinking of the individual polymer units. Using theamines listed, olefin/MA copolymers (MA=maleic anhydride) functionalizedto the half-amide are obtained at reaction temperatures of at most50-60° C. Above 50° C., imide formation arises to an increased extent,meaning that, should olefin/MA copolymers functionalized to the imide bedesired, it is preferable to carry out the reaction in the temperaturerange from about 50 to about 150° C.

The reactions to give the half-esters, half-amides and imides can becarried out either without a diluent, or else in a solvent, preferablyin the mineral oil used for formation of the explosive emulsion. Thelatter is particularly preferred, in cases where the viscosity of theemulsifier permits it.

The emulsifiers according to the invention can be mixed with any commonemulsifier. Preferred mixing components are the water-in-oil emulsifiersused in U.S. Pat. No. 3,447,978, such as sorbitan monooleate,glycerides, phosphoric esters, etc., but also amidoamines/imidazolinesobtainable by condensation of fatty acids with polyamines. Particularpreference is given to mixtures of the emulsifiers according to theinvention with the monomeric emulsifiers specified in EP-A-0 155 800 andEP-A-0 285 608, i.e. with derivatives of alkenylsuccinic anhydrides,such as polyisobutenylsuccinic anhydride, i.e. half-esters, half-amides,imides and salts thereof with amines and alkali metals.

The emulsifiers according to the invention are suitable for use asconstituent C in the explosive compositions (emulsion explosives) of theinvention. The salt phase of the emulsion explosive (constituent A)consists of a supersaturated solution of an oxygen-releasing salt,ammonium nitrate preferably being used. Other oxygen-releasing salts,e.g. other nitrates such as sodium or potassium nitrate, and alsoperchlorates can also be used as additives.

The oil phase (constituent B) used is generally a mineral oil, inparticular a paraffin mineral oil. It is also possible to usenaphthene-based oils, vegetable oils, used oil or diesel oil. Theemulsifiers used are mostly predissolved in the oil phase. Theemulsifiers can be used as concentrate (up to 100% of active substance)or else as solution in a suitable oil, in cases where the inherentviscosity of the emulsifier is too high.

Further auxiliaries are bodying agents such as waxes, paraffins orelastomers, in cases where the intention is to prepare cartridgedexplosive, products which are said to increase the water resistance ofthe emulsion, such as silicone oils, but also other emulsionstabilizers, thickeners or antioxidants, which are intended to preventaging of the emulsifier.

The explosive emulsion generally comprises 20-97% by weight, preferably30-95% by weight, particularly preferably 70-95% by weight, of thediscontinuous phase (i.e. predominantly water and ammonium nitrate withthe other water-soluble additives), and the water content varies in therange 2-30%, preferably in the range 4-20%. The oil phase (including theadditives dissolved therein) includes about 1-20% by weight of theoverall composition, but preferably 1-10%. The content of emulsifier inthe overall composition is in the range 0.2-5% by weight, preferably inthe range 0.4-3%.

The explosive emulsions are preferably prepared using common emulsifyingprocesses. Firstly, a supersaturated ammonium nitrate solution(optionally with the addition of other water-soluble auxiliaries listedabove) at 80-100° C. is prepared and heated until all solids aredissolved, and, if necessary, the solution is filtered to removeinsoluble material. In parallel, a solution of the emulsifier in the oilmatrix (likewise with the addition of other oil-soluble auxiliaries suchas waxes, paraffins, antioxidants etc.), likewise at 50-100° C., isprepared. Then, with stirring, the salt melt is preferably added to theoil/emulsifier mixture, but the reverse procedure is also possible.Vigorous stirring increases emulsion formation. The entrainment of seedcrystals into the emulsion must be avoided. Where appropriate, othercomponents, such as microballoons (glass bubbles), solids such as TNT,solid fuels such as aluminum or sulfur, inert materials such as baryteor sodium chloride, or undissolved ammonium nitrate are then added, andthe mixture is stirred until the solids are distributed homogeneously.Chemical gassing involves adding, for example, thiourea and sodiumnitrite, which leads to gassing of the emulsion within a certain period.In industry, the emulsification stage can be carried out in specialmixers and, where appropriate, using static mixers.

The invention further provides a terpolymer comprising monomer unitsderived from

A) an olefin having more than 40 carbon atoms,

B) maleic anhydride, and

C) an alkylallyl polyglycol ether of the formula

R—(OCH₂CH₂)_(n)O—CH₂—CH═CH₂

where n=3-20 and R=C₁-C₄-alkyl.

The olefin preferably has from 40 to 500, in particular from 40 to 200,carbon atoms. It is preferably an α-olefin, particularly preferably apolyisobutene. A particularly preferred embodiment relates to modifiedterpolymers obtained by polymer-analogous reaction of the saidterpolymers with alcohols, amines and aminoalcohols. The terpolymersaccording to the invention are used as emulsifiers in explosivecompositions.

Particularly preferred terpolymers comprise monomer units of

A) 18 to 70 mol % of polyisobutene

B) 25 to 80 mol % of maleic anhydride

C) 2 to 15 mol % of allyl polyglycol ether.

As the experimental examples listed below demonstrate, the polymericemulsifiers according to the invention, alone or in particular in amixture with other emulsifiers, such as, for example, sorbitan esters,exhibit identical emulsion stabilities to a conventionalpolyisobutenylsuccinic acid derivative. It is interesting that thefunctionalization of the polymeric anhydride, at least in mixtures withother emulsifiers, is not absolutely necessary. Under the conditions ofthe emulsification, the corresponding amide presumably forms from theanhydride and ammonium nitrate in situ.

EXAMPLES

Synthesis of the Polymeric Emulsifier

Example 1 Copolymer of Maleic Anhydride and Polyisobutylene

A 2 l four-necked flask fitted with a stirrer was charged with 900 g(0.90 mol) of a polyisobutylene with a molecular weight of 1000 g/moland 88.2 g (0.90 mol) of maleic anhydride; the charge was heated to 100°C. The system was then evacuated 3× up to 100 mbar and aerated in eachcase with nitrogen in order to render it inert. The contents were heatedto 115° C. and 9.9 g (1% by weight) of di-tert-butyl peroxide wereadded. The reaction mixture was heated further to 150° C., and thereaction temperature increased briefly to 160° C. The system was thenmaintained for 4 h at 150° C. Then, at 150° C., a reduced pressure of 20mbar was applied, although no distillate was obtained. Cooling gave 986g of a yellowish oil with a viscosity of 4.1 Pas at 80° C. (Bohlin, 10s⁻¹).

Molecular weight (GPC): Mn=1608 g/mol, Mw=3621 g/mol

Residual olefin content: 48%

Example 2 Copolymer of Maleic Anhydride, Polyisobutylene andC₁₈-α-Olefin

A 1 l four-necked flask fitted with stirrer was charged with 600 g (0.60mol) of a polyisobutylene with a molecular weight of 1000 g/mol, 50 g(0.2 mol) of a C₁₈-α-olefin and 78.4 g (0.80 mol) of maleic anhydride;the contents were heated to 100° C. The system was then evacuated 3× upto 100 mbar and aerated each time with nitrogen to render it inert. Thecontents were heated to 120° C., and 7.3 g (1% by weight) ofdi-tert-butyl peroxide were added. The reaction mixture was heated againto 150° C., and the reaction temperature increased briefly to 160° C.The system was then maintained for 4 h at 150° C. Then, at 150° C., areduced pressure of 20 mbar was applied, although no distillate wasobtained. Cooling gave 725.8 g of an orange-red oil with a viscosity of4.0 Pas at 80° C. (Bohlin, 10 s⁻¹).

Example 3 Copolymer of Maleic Anhydride, Polyisobutylene and AllylmethylPolyglycol Ether With a Molecular Weight of 334 g/mol

A 2 l four-necked flask fitted with stirrer was charged with 1200 g(1.20 mol) of a polyisobutylene with a molecular weight of 1000 g/mol,133.6 g (0.4 mol) of allylmethyl polyglycol ether and 156.8 g (1.60 mol)of maleic anhydride; the contents were heated to 100° C. The system wasthen evacuated 3× up to 100 mbar and aerated each time with nitrogen torender it inert. The contents were heated to 120° C., and 14.9 g (1% byweight) of di-tert-butyl peroxide were added. The reaction mixture wasagain heated to 150° C., and the reaction temperature increased brieflyto 155° C. The system was then maintained for 4 h at 150° C. Then, at150° C., a reduced pressure of 30 mbar was applied, and 4.0 g ofdistillate were obtained. Cooling gave 1469.6 g of a yellowish oil witha viscosity of 3.6 Pas at 80° C. (Bohlin, 10 s⁻¹).

Molecular weight (GPC): Mn=1540 g/mol, Mw=3460 g/mol

Residual olefin content: 52%

Example 4 Reaction of Example 1 With Diethylaminoethanol

A 2 l four-necked flask fitted with stirrer was charged with 312 g of aparaffinic mineral oil and 657 g of the copolymer from Example 1; thecontents were heated to 90° C. Over the course of 10 min, 70.3 g (0.6mol) of N,N-diethylethanolamine were added dropwise, and the mixture wasstirred for 5 h at 90° C. This gave 1036 g of a yellow oil.

Example 5 Reaction of Example 2 With Diethylaminoethanol

A 2 l four-necked flask fitted with stirrer was charged with 175.6 g ofa paraffinic mineral oil and 362.9 g of the copolymer from Example 2;the contents were heated to 90° C. Over the course of 10 min, 46.9 g(0.4 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 582.4 g of a brown oil.

Example 6 Reaction of Example 3 With Diethylaminoethanol

A 2 l four-necked flask fitted with stirrer was charged with 355.1 g ofa paraffinic mineral oil and 734.8 g of the copolymer from Example 3;the contents were heated to 90° C. Over the course of 10 min, 93.8 g(0.6 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 1180.6 g of a red-brownoil.

Example 7 Comparative Example

This emulsifier was obtained by reacting a polyisobutyenylsuccinicanhydride (molecular weight of the parent polyisobutene: 950 g/mol) withone mole equivalent of 2-diethylaminoethanol at 90° C.

Example 8 Comparative Example

The comparative emulsifier used was a commercially available sorbitanmonooleate.

Example 9 Comparative Example

This emulsifier was obtained by condensation of tall oil fatty acid andtriethylenetetramine in the molar ratio 3:1 at 230° C. and at a reducedpressure of 20 mbar.

Example 10

The emulsifier of Example 4 was mixed in the mass ratio 80:20 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 7 and homogenized at 60° C.

Example 11

The emulsifier of Example 4 was mixed in the mass ratio 80:20 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 8 and homogenized at 60° C.

Example 12

The emulsifier of Example 4 was mixed in the mass ratio 50:50 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 7 and homogenized at 60° C.

Example 13

The emulsifier of Example 1 was mixed in the mass ratio 50:50 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 7 and homogenized at 60° C.

Example 14

The emulsifier of Example 5 was mixed in the mass ratio 50:50 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 7 and homogenized at 60° C.

Example 15

The emulsifier of Example 6 was mixed in the mass ratio 50:50 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 7 and homogenized at 60° C.

Example 16

The emulsifier of Example 4 was mixed in the mass ratio 90:10 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 8 and homogenized at 60° C.

Example 17

The emulsifier of Example 4 was mixed in the mass ratio 90:10 (takinginto consideration the active substance content) with the comparativeemulsifier of Example 7 and homogenized at 60° C.

Example 18 Copolymer of Maleic Anhydride and Polyisobutene

A 2 l four-necked flask fitted with stirrer was charged, under anitrogen atmosphere, with 700 g (0.70 mol) of a polyisobutylene with amolecular weight of 1000 g/mol, 500 g of 1,2-dichloroethane, 68.6 g(0.70 mol) of maleic anhydride and 7.7 g of tert-butyl perbenzoate; thecontents were heated to 80° C. The reaction mixture was in the form of aclear solution. The system was then maintained for 33 h at 80° C. Then,at 150° C. and a maximum reduced pressure of 20 mbar, 1,2-dichloroethaneand excess maleic anhydride were distilled off. Cooling gave 745 g of ayellowish, high-viscosity oil.

Molecular weight (GPC): Mn=1949 g/mol, Mw=5081 g/mol.

Residual olefin content: 66%

Example 19 Copolymer of Maleic Anhydride and Polyisobutene

A 2 l four-necked flask fitted with stirrer was charged, under anitrogen atmosphere, with 800 g (0.80 mol) of a polyisobutylene with amolecular weight of 1000 g/mol, 545 g of xylene, 78.4 g (0.80 mol) ofmaleic anhydride and 8.8 g of tert-butyl perbenzoate; the contents wereheated to 80° C. The reaction mixture was in the form of a clearsolution. The system was then maintained for 30 h at 80° C. Then, at amaximum of 200° C. and a maximum reduced pressure of 20 mbar, xylene andexcess maleic anhydride were distilled off. Cooling gave 869 g of ayellowish, high-viscosity oil.

Molecular weight (GPC): Mn=1820 g/mol, Mw=4520 g/mol

Residual olefin content: 56%

Example 20 Copolymer of Maleic Anhydride and Polyisobutene

A 2 l four-necked flask fitted with stirrer was charged with 1000 g(1.00 mol) of a polyisobutylene with a molecular weight of 1000 g/mol,127.4 g (1.30 mol) of maleic anhydride and 538 g of xylene; the contentswere heated to 100° C., and the system was rendered inert by evacuating3× up to a reduced pressure of 300 mbar and aerating with nitrogen. At120° C., 11.3 g of di-tert-butyl peroxide were then added over thecourse of 5 min, and the reaction mixture was heated to 145° C.(reflux). The system was then maintained for 4 h at this temperature.Then, at a maximum of 200° C. and a maximum reduced pressure of 20 mbar,xylene and excess maleic anhydride were distilled off. Cooling gave 1137g of a yellowish, high-viscosity oil.

Molecular weight (GPC): Mn=1352 g/mol, Mw=2520 g/mol

Residual olefin content: 38.5%

Example 21 Reaction of Example 18 With Diethylethanolamine

A 1 l four-necked flask fitted with stirrer was charged with 270 g of aparaffinic mineral oil and 571 g of the copolymer of Example 18; thecontents were heated to 90° C. Over the course of 10 min, 58.6 g (0.5mol) of N,N-diethylethanolamine were added dropwise, and the mixture wasstirred for 5 h at 90° C. This gave 896 g of a yellow oil.

Example 22 Reaction of Example 19 With Diethylethanolamine

A 2 l four-necked flask fitted with stirrer was charged with 305 g of aparaffinic mineral oil and 654 g of the copolymer from Example 19; thecontents were heated to 90° C. Over the course of 10 min, 58.6 g (0.5mol) of N,N-diethylethanolamine were added dropwise, and the mixture wasstirred for 5 h at 90° C. This gave 1015 g of a yellow oil.

Example 23 Reaction of Example 20 With Diethylethanolamine

A 1 l four-necked flask fitted with stirrer was charged with 212 g of aparaffinic mineral oil and 437 g of the copolymer from Example 20; thecontents were heated to 90° C. Over the course of 10 min, 58.6 g (0.5mol) of N,N-diethylethanolamine were added dropwise, and the mixture wasstirred for 5 h at 90° C. This gave 701 g of a yellow, clear oil.

Example 24

The emulsifier of Example 21 was mixed in the mass ratio 50:50 with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 25

The emulsifier of Example 22 was mixed in the mass ratio 50:50 with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 26

The emulsifier of Example 23 was mixed in the mass ratio 50:50 with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Determination of the molecular weights of the base polymers (Examples1-3, 18-20): The molecular weights were determined by gel permeationchromatography (GPC) using tetrahydrofuran as eluent againstpolyisobutene as standard; the values given were for Mn and Mw. Themolecular weight determinations include the unreacted polyisobutenepresent in the polymeric anhydride. The actual molecular weights of thepolymeric anhydride are accordingly considerably higher.

Determination of the residual olefin content (Examples 1-3, 18-20):About 5-10 g of the polymeric anhydrides were chromatographed over 100 gof silica gel 60 using pentane as the eluent. The residual olefin iseluted here with an R_(F) value of about 0.9. The correspondingfractions were combined, the solvent was distilled off and the residuewas weighed.

Preparation of the Test Emulsion

The test emulsion used has the following composition:

1.0 g of emulsifier (100% of active substance not taking intoconsideration the oil content)

6.3 g of white oil

81.0 g of ammonium nitrate

12.0 g of water

The white oil together with the emulsifier is introduced at 80° C. intoa tall 250 ml beaker and, with stirring using a stainless steel anchorstirrer which passes close to the wall and with an increasing stirringrate from 800 to 2000 rpm, the clear, hot ammonium nitrate/water melt ata temperature of from 95 to 98° C. is introduced. The melt is initiallyadded dropwise and then added in one portion over 15 seconds from anarrow-necked 100 ml Erlenmeyer flask such that it can be stirred in thecenter of the stirrer blade; the melt must not solidify on the wall. Theresulting, transparent emulsion is then stirred at 80° C. for from 3 to5 min and drawn off while still hot (without any crystals which may haveformed).

Emulsion Stability

The shelf life of the prepared emulsions was investigated a) at roomtemperature (about 20-25° C.) and also b) during storage at fluctuatingtemperatures (alternating in each case for 24 h at 0° C. and 40° C.).The assessment was visual; the emulsion was no longer regarded as stableif seed crystals had visibly formed.

Storage stability at Storage stability at fluctuating Polymer MixingEmulsifier RT (d) temperatures (d) component Additive ratio Example 1 00 Example 2 0 0 Example 3 0 0 Example 4 >30 2 Example 5 >30 2 Example 60 0 Example 7 >30 >30 (Comp.) Example 8 6 4 (Comp.) Example 9 6 1(Comp.) Example 10 >30 >30 Example 4 Example 7 80:20 Example 11 >30 >30Example 4 Example 8 80:20 Example 12 >30 >30 Example 4 Example 7 50:50Example 13 >30 >30 Example 1 Example 7 50:50 Example 14 >30 >30 Example5 Example 7 50:50 Example 15 >30 >30 Example 6 Example 7 50:50 Example16 >30 >30 Example 4 Example 8 90:10 Example 17 >30 >30 Example 4Example 7 90:10 Example 24 >30 >30 Example Example 7 50:50 21 Example25 >30 >30 Example Example 7 50:50 22 Example 26 >30 >30 Example Example7 50:50 23

What is claimed is:
 1. A terpolymer comprising monomer units derivedfrom A) an olefin having more than 40 carbon atoms, B) maleic anhydride,and C) an alkylallyl polyglycol ether of the formulaR—(OCH₂CH₂)_(n)O—CH₂—CH═CH₂ where n=3-20 and R=C₁-C₄-alkyl.
 2. Aterpolymer obtained by polymer-analogous reaction of terpolymers asclaimed in claim 1 with alcohols, amines, ammonia or aminoalcohols.